Composition

ABSTRACT

A HYDROCARBON GASOLINE COMPOSITION CONTAINING, AS AN ADDITIVE, A MINOR AMOUNT, SUFFICIENT TO IMPROVE THE DETERGENCY OF SAID GASOLINE, OF THE REACTION PRODUCT OF: (A) A MONOCARBOXYLIC ACID OR DERIVATIVE THEREOF; (B) A POLYAMINE HAVING AT LEAST THREE NITROGEN ATOMS, AT LEAST TWO PRIMARY AND AT LEAST ONE SECONDARY; (C) AN ALKYL-SUBSTITUTED PHENOL; AND (D) FORMALDEHYDE; A PREFERRED REACTION PRODUCT CONTAINS 4,7,10-TRIS(2-HYDROXY-5-ALKYL) BENZYLTERTRAETHYLENEPENTAMINE-1,13 PALMITIC ACID DIAMIDE.

United States Patent 3,701,640 COMPOSITION Charles A. Lease, Chicago,Seymour H. Patinkin, Skokie, and Frank J. Chloupek, South Holland, 11].,assignors to Atlantic Richfield Company, New York, N.Y.

No Drawing. Continuation of application Ser. No.

44,612, June 8, 1970, now abandoned. This application Nov. 5, 1971, Ser.No. 196,241

Int. Cl. C101 N22 US. CI. 44-66 20 Claims ABSTRACT OF THE DISCLOSURE Ahydrocarbon gasoline composition containing, as an additive, a minoramount, sufiicient to improve the detergency of said gasoline, of thereaction product of:

(A) a monocarboxylic acid or derivative thereof;

(B) a polyamine having at least three nitrogen atoms,

at least two primary and at least one secondary;

(C) an alkyl-substituted phenol; and

(D) formaldehyde;

A preferred reaction product contains 4,7,l0-tris(2-hydroxy-S-alkyl)benzyltetraethylenepentamine-l,1 3 palmitic acid diamide.

This application is a continuation of Ser. No. 44,612, filed June 8,1970, now abandoned.

The present invention is directed to novel hydrocarbon gasolinecompositions having improved detergency. More specifically, the presentinvention concerns the use as gasoline additives of reaction products ofa monocarbox ylic acid or derivatives thereof, an alkyl-substitutedphenol, a polyamine having at least three nitrogen atoms, at least twoprimary and at least one secondary, and formaldehyde and the modifiedderivatives thereof wherein the phenolic hydrogen is replaced by othergroups.

Recently, increased engine deposits due largely to various emissioncontrol devices required on automobiles have been encountered in severalcritical engine areas. For instance, deposit build-ups occur in the PCVdevice and carburetor. These deposits upset normal PCV flow, idlingspeed and the air-fuel ratio; additionally, these deposits, aggravatefurther engine deposits such as sludge and varnish in the crankcase,piston, and rocker arm areas. This invention, however, provides gasolinedetergent additives which reduce engine deposits even while operatingwith modern emission control devices.

In accordance with the present invention, it has been found that thereaction products of a monocarboxylic acid or a derivative thereof, analkyl-substituted phenol, a polyamine having at least three nitrogenatom, at least two primary and at least one secondary, and formaldehyde,and the modified derivatives thereof wherein the phenolic hydrogen isreplaced by other groups, provide compositions having excellentdetergency when added to hydrocarbon gasolines in small amounts. Anadvantageous modification of the phenolic hydroxyl group of thesereaction products is accomplished by the partial or completeneutralization thereof with basic materials, for instance ammonium andmetal components such as their hydroxides, carbonates and bicarbonates.Metals of Groups IB, II-A, H-B, IV-A, V-A and VIII, e.g. calcium,nickel, zinc, barium, iron, copper, cobalt, tin, lead and bismuth, areparticularly useful. Specific, exemplary compounds which can be used toaccomplish the neutralization of the phenolic hydroxyl group areammonium hydroxide, calcium hydroxide, nickel hydroxide, zinc carbonate,iron carbonate, copper carbonate and cobalt bicarbonate. Anothermodification of the phenolic hydroxyl group is accomplished by theesterification or etherifica tion thereof. The phenolic hydroxyl groupmay be esterified or etherified either prior or subsequent, preferablyprior, to the formation of the reaction products described herein.Suitable acids and alcohols useful in this modification often contain upto about -8 carbon atoms, e.g. acetic, propionic or butyri-c acids andmethanol or ethnol. The esterification and etherification areaccomplished by methods well known in the art.

The sequence in which the reactants can be combined to afford thegasoline detergent additives of the present invention may be varieddepending upon the products which are being prepared. Regardless of thesequence of reaction and reaction conditions, however, about 0.05 to 2moles, preferably about 0.2 to 1 mole, of reactive carboxylic acid group(including an anhydride group as two such carboxyl groups) is generallyreacted per average basic, reactive primary nitrogen atom present in onemole of the amine; and at least about 0.2 mole, preferably up to about 2moles, of each of the alkylated phenol and formaldehyde per averagebasic reactive, secondary nitrogen atom present in a mole of aminereactant, is reacted. Advantageously, each of the alkylated phenol andformaldehyde is reacted in an amount of about 0.2 to 1 mole per averagebasic reactive, secondary nitrogen atom per mole of the amine.

The four reactants which are employed to form the reaction products ofthe invention will be described under separate headings.

THE MONOCARBOXYLIC ACID REACTANT The carboxylic acid useful in thepresent invention is a monocarboxylic acid of from 2 to about 24 carbonatoms including the corresponding acid anhydrides, esters or acidhalides, e.g. acid chlorides, of the carboxylic acids. The acid can bestraight chain or branched, saturated or unsaturated, aliphatic(including cycloaliphatic), aromatic or heterocyclic. The preferredcarboxylic acids are the ali phatic monocarboxylic acids of 4 to about24 carbon atoms. Particularly suitable monocarboxylic acids andanhydrides are the saturated and unsaturated fatty acids, preferably ofabout 10 to 24 carbon atoms, such as lauric acid, stearic acid, palmiticacid, oleic acid, arachidic acid, myristic acid, linoleic acid and thelike acids or mixtures thereof.

POLYAM-INE REACTANT The amine component of the reaction products of theinvention is a polyamine having at least three nitrogen atoms, at leasttwo primary and at least one secondary. Suitable polyamines of theinvention include polyalkylene polyamines represented by the formula:

wherein n is a number of at least 2, commonly 2 to 10; R is an alkyleneradical of 2 to about 25 carbon atoms,

preferably 2 to about '8 carbon atoms. Non-limiting examples of thepolyalkylenepolyamine reactants are diethylenetriamine;triethylenetetramine; tetraethylenepentamine; etc.

FORMALDEYHYDE REACTANT The formaldehyde component may be present in anyavaiable form of formaldehyde such as formalin, paraformaldehyde andsuch.

THE ALKYLAT'E'D PH ENOL sulting product with the fourth component, e.g.,the acid component, is generally carried out at a temperature of about200 to 230 C., with the optimum reaction temperature being dependentprimarily on the particular acid component selected. Again, thereactions proceed readily at atmospheric pressure, although subandsuperatmospheres of pressure can be utilized.

Numerous other ramifications of these methods can be used for preparingthe additives of the invention. For example, in many instances, morethan one monocarboxylic acid or anhydride reactant may be reacted withone or more of the polyamines of the invention. In addition, reactionproducts of the monocarboxylic acid component and the polyamine may befurther reacted with phenolic condensation compounds of the polyamine,phenol and formaldehyde reactants in varying stoichiometric ratioswithin those described hereinabove.

The following is illustrative of the reactions that may be employed toproduce the reaction products used in the gasoline compositions of thepresent invention.

(A) Monocarboxylic acid-l-polyalkylene polyamine with formaldehyde andalkyl phenol.

phenol, octyl phenol, nonyl phenol, p-tert-octyl phenol, l,l,3,3tetramethylbutyl, phenol, a mixture of such phenols, and the like. Ifdesired, the alkylated phenols may also contain one or morenon-deleterious substituent groups. The present invention alsocontemplates use as the phenol component, aromatic derivatives otherthan phenyl derivatives as, for instance, alkylnaphthols and similarderivatives of biphenyl, terphenyl, phenanthrene, anthracene, etc.

As discussed above, the sequence of reaction can vary. For instance, themonocarboxylic acid reactant may first be reacted with the polyaminecomponent and the resulting product then reacted directly with thephenol component and the formaldehyde component. Reaction of the acidand amine may be conducted at a reaction temperature of about 1125 to350 C., preferably about 190 to 280 C. Reaction of the resulting productwith the phenol and the formaldehyde is usually conducted at atemperature of about 125 to 350 C., preferably about 190 to 280 C. Bothof the reactions are conveniently carried out at atmospheric pressurebut subor super-atmospheric pressures can be employed, if desired. Thereaction may be carried out in bulk or in the presence of a mutualsolvent for the reactants.

Alternatively, the polyamine, phenol and formaldehyde can be reactedfirst and the condensation product of the three then reacted with theacid component which is preferably a fatty acid. Reaction of thepolyamine, phenol and formaldehyde components can be carried outconveniently by heating the three-component mixture at a temperature ofabout 70 to 150 C. until essentially all water of reaction is removed.Reaction of the re- 3CH2O OH CH, N CHZCH The above scheme indicatesthat, for instance, if only one mole of formaldehyde and reactive phenolwere used that only one benzyl alcohol grouping would be substituted onthe reactive amino groups. Additionally, if an excess of mono carboxylicacid were used both primary reactive amino groups of the polyalkyleneamine could form amide groups therewith. Thus, the final condensationproducts are normally mixtures of various reaction products dependent toa substantial extent upon the reaction conditions and mole ratios ofvarious reactants.

The condensation products used in the gasoline compositions of thisinvention are characterized as having at least one reactive phenolichydroxy group which remains unsubstituted or is modified with variousgroups as previously indicated. The gasoline-soluble metal salts,particularly the calcium salts, are particularly eflective for thepurposes of this invention. The salts can be prepared by neutralizationof the condensation product with a basic compound of the metal as, forinstance, the hydroxides, oxides, carbonates and the like or byneutralization with ammonium hydroxide followed by preparation of themetal salt by methathesis. Greater than stoichiometric equivalents ofthe metals can be used, if desired. to give basic salts.

By the term gasoline to which the additives of the present invention areincorporated is meant hydrocarbon fractions boiling primarily in thegasoline range, usually in the range of about to 425 F., often havingadded thereto a small amount, generally between about 1 to 6 cc. pergallon, preferably about 2 to 4 cc. per gallon, of a tetra-lower-alkyllead compound as an anti-knock agent. The gasolines are usually composedof a major amount of a blend of hydrocarbon mineral oil fractionsboiling primarily in the aforementioned range and will contain varyingproportions of parafiins, olefins, napthenes and aromatics derived bydistillation, cracking and other refining and chemical conversionprocesses practiced upon crude oil fractions. Straight run gasolines,gasolines derived from cracking gas oil, gasolines or reformate fromreforming straight run naphtha over a platinum-alumina catalyst in thepresence of hydrogen, etc., are components frequently used in making upa gasoline composition. A typical premium gasoline, besides containing asmall amount of a tetra-lower-alkyl lead compound as an antiknock agentmay also contain small amounts of other nonhydrocarbon constitutentsused to impart various properties to the gasoline in its use in internalcombustion engines, e.g., halohydrocarbon scavengers, oxidation,inhibitors, etc. Such gasolines frequently have a Research Method octanenumber of about 90 and 105, and a Motor Method octane number of about 80to 98.

The reaction products described herein are incorporated in the gasolinein minor amounts sutficient to provide a composition exhibiting improveddetergent properties. The actual amount of the additive employed mayvary depending upon the particular gasoline employed, its lead content,etc. Often about 10 to 500 or more pounds of the detergent, preferablyabout 15 to 100 or 400 pounds per 1,000 barrels of gasolinne, areemployed.

The following examples further illustrate the present invention.

EXAMPLE I Preparation of the reaction product of palmitic acid,octylphenol, formaldehyde and tetraethylene pentamine Product A of thepresent invention can be prepared in the following manner:

Palmitic acid (768 g.), tetraethylenepentamine (284 g.) and 99 g. ofmineral lubricating oil having a viscosity of 1505 SUS at 100 F. areintroduced into a -liter, fournecked, round-bottom flask fitted with amechanical stirrer, water separator, reflux condenser, thermometer, andnitrogen gas inlet. The mixture is heated and stirred for about 4 hoursunder a nitrogen blanket at about 100 C. The temperature is increased toabout 150 C. over a twoand-one-half-hour period and 50 g. of water iscollected (pH =11). The mixture is then allowed to cool overnight.Octylphenol (927 g.) and 750 g. of the same mineral oil are added to thereaction mixture and the mixture is heated to 90 C. Formaldehydesolution (38%, 366 g.) is added dropwise with stirring over aboutone-and-onehalf hours. Stirring is maintained throughout the additionand the temperature is held at 90-95 C. for an additionaltwo-and-one-half hours. The temperature is then slowly increased to 150C. and 292 g. of water are collected (pI-I =5), leaving the productdesignated A having a major component of the following formula:

about one-and-one-half hours. The mixture is stirred at 85 C. for 5hours and then slowly heated to 150 C. Water g., pH=11) is collected,240 g. of mineral lubricating oil having a viscosity of 150 SUS at F.added, and the mixture is then allowed to cool overnight. The mixture isdiluted with 3 liters of benzene and filtered. The benzene is flashdistilled off, giving 3828 g. of product.

EXAMPLE III Zinc neutralized A Product A is heated with stirring to 80C. and 50 g. of water is added. Zinc carbonate (124 g.) is then addedportionwise over about one-and-one-half hours. The reaction mixture isstirred an additional 3 hours at 80 C., and then slowly heated to 150 C.After cooling overnight, 3 liters of benzene are added and the mixturefiltered. The benzene is then flash distilled ofi, giving 3816 g. ofproduct.

EXAMPLE IV Calcium neutralized A Product A is heated with stirring to 80C. and 50 g. of water is added. Calcium hydroxide (75 g.) is then addedportionwise over about one-and-one-half hours. The reaction mixture isstirred an additional 5 hours at 80 C. and then slowly heated to 150 C.After cooling overnight, 3 liters of benzene are added and the mixturefiltered. The benzene is then flash distilled off, giving about 3800 g.of product.

EXAMPLE V Nickel neutralized A" Product A is heated with stirring to 80C. and 50 g. of water is added. Nickel hydroxide (66 g.) is then addedportionwise over about one-and-one-half hours. The reaction mixture isstirred an additional 5 hours at 80 C. and then slowly heated to 150 C.After cooling overnight, 3 liters of benzene are added and the mixturefiltered. The benzene is flash distilled 01f, giving 3800 g. of product.

In addition to the salts described above, other useful salts of thereaction product of Example I which can be prepared are those of copperand other metals.

EXAMPLE VI The additives of present invention were evaluated in a96-hour cycling test using a 1966 Chevrolet V-8 engine. To aggravateengine dirtiness, a slipsteam of exhaust gases was routed to the intakeair cleaner. This flow and the PCV flow were adjusted to the same levelat the start of each test, but then not further adjusted during thetest.

0 I ll CHKCHQHNHCH2CH2NCH2CH2NCHQCHaNCHzCHzNC (CH2)14CH3 I CH2 OR OR ORR R R wherein R is hydrogen and R is 1,1,3,3-tetramethylbutyl. ExamplesII through V describe product A modified with various neutralizationagents.

EXAMPLE II Ammonium neutralized A Product A is heated with stirring to80 C. and 125 g. of 28% ammonium hydroxide solution is added over Theengine was completely overhauled (cleaned) between tests and a new PCVdevice installed. The PCV was 0 checked for deposit plugging at 24-hourintervals in a A commercial type laboratory leaded gasoline.

fuel plus 35 pounds of Calcium Neutralized Product A/ 1000 bbl.gasoline.

A commercial type laboratory leaded gasoline.

The differences in hour determinations reflect normal manufacturingtolerances in the new PCV devices used in the individual tests.Comparisons of data in the table show little change in flow (littledeposit plugging) during the tests when the additive was used. Forexample, at 20 vacuum, 2.09 ftfi/min. flowed through the valve at theend of Test 3 compared to 2.11 at the start. In contrast, there wereobserved substantial changes in flow (indicating deposit plugging) onthe tests without the additive. Again, at 20" vacuum, the flow droppedfrom 2.08 to 1.09 in Test 1 and from 2.00 to 1.41 in Test 4.

EXAMPLE VII A visual rating system provides another method ofevalulating effectiveness of detergents. This rating system, shown inTable II, .was carried out at the conclusion of the test, after theengine was disassembled. A rating of indicates a perfectly clean part orsurface, and lower numbers indicate respective degrees of dirtiness.

ortho or para position, an alkyl ester of said alkylated phenol, andalkyl ether of said alkylated phenol and mixtures thereof, said esterand ether linkages containing up to about 8 carbon atoms; and

(D) formaldehyde; wherein about 0.05 to 2 moles of reactive carboxylicacid group is reacted per average, reactive primary nitrogen atom permole of component B, and components C and D are each reacted in anamount of about 0.2 to 2 moles per average basic, reactive secondarynitrogen atom per mole of component B.

2. The composition of claim 1 wherein said component C is an alkylatedphenol having at least one alkyl group of about 4 to about 20 carbonatoms and at least one reactive ortho or para position.

3. The composition of claim 2 wherein component A is a fatty acid ofabout 10 to 24 carbon atoms.

4. The composition of claim 2 wherein component B is a polyalkylenepolyamine of the formula:

wherein n is from 2 to about 10 and R is alkylene of 2 to about 8 carbonatoms.

5. The composition of claim 2 wherein about 0.2 to 1 mole of reactivecarboxylic acid group is reacted per average, reactive primary nitrogenatom per mole of component B.

6. The composition of claim 2 wherein the phenolic hydroxyl group of thereaction product is modified to form ammonium or metal salts thereof.

7. The composition of claim 2 wherein about 10 to 500 pounds of reactionproduct are present per one thousand barrels of gasoline.

TABLE II Cleanliness ratings Rocker arm covers Right Left Pan Piiton sirt Detergent additive Varnish Sludge Varnish Sludge Varnish Sludgevarnish None 10 9. 5 10 9. 5 10 9. 7 9.9 +35# /M bbl. calcium neutrahzedProd A 10 10 10 10 10 9.9 9.9 -do 10 10 10 10 10 10 9. 9 +None 10 9. 39. 8 9. 1 10 9. 7

Commercial-type laboratory leaded gasoline.

EXAMPLE III 8. The composition of claim 2 wherein the phenolic Inaddition to the rating tests of the previous examples, comparativephotographs were taken of engine parts following the use of fuelcontaining calcium neutralized Product A as compared to fuel withoutcalcium neutralized Product A. In the test, using the calcium modifiedProduct A, the rocker-arm covers and pan were decidedly cleaner than inthe test without calcium-modified Product A.

I claim:

1. A gasoline composition comprising a hydrocarbon gasoline and a minoramount, sutficient to improve the detergent properties of said gasoline,of an additive which is the reaction product of:

(A) monocarboxylic acid of 2 to about 24 carbon atoms;

(B) polyamine having at least three nitrogen atoms,

at least two primary and at least one secondary;

(C) a component selected from the group consisting of an alkylatedphenol having at least one alkyl group of about 4 to 20 carbon atoms andat least one reactive hydroxyl group of said reaction product ismodifiedto form an alkyl ester or alkyl etherthereof, said alkyl esterand alkyl ether containing up to about 8 carbon atoms.

9. The composition of claim 1 wherein component A is a fatty acid whichcontains from about 10 to 24 carbon atoms; component B has a formula asfollows:

18. The composition of claim 2 wherein a major component of saidreaction product has the following formula:

OH OH OH 10. The composition of claim 9 wherein R contains from 2 toabout 10 carbon atoms and component C is said para alkyl substitutedphenol.

11. The composition of claim 10 wherein the gasoline detergent additiveis a metal or ammonium salt of the phenolic hydroxyl group of thereaction product.

12. The composition of claim 10 wherein said phenolic hydroxyl group ofsaid reaction product is modified to form an alkyl ester or alkyl etherthereof, said alkyl ester and alkyl ether containing up to about 8carbon atoms.

13. The composition of claim 11 wherein the metal is calcium.

14. The composition of claim 11 wherein the metal is nickel.

15. The composition of claim 11 wherein the metal is 16. The compositionof claim 10 wherein the reaction product contains a major portion of a4,7,10-tri(2-hydroxy-S-alkyl)benzyltetraethylenepentamine-1,13 palmiticacid diamide.

17. The composition of claim 10 wherein about 10 to 500 pounds ofreaction product are present per one thousand barrels of gasoline.

References Cited UNITED STATES PATENTS 3,498,766 3/1970 Gee et al 44-683,280,097 10/1966 Cizek 260- 4045 3,279,901 10/ 1966 Robbins et a1 4466DANIEL E. WYMAN, Primary Examiner Y. H. SMITH, Assistant Examiner U.S.Cl. X.R.

zg gy UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.40 Dated October 31, 1972 Inventor(s)CharleS A. Lease Seymour H.Patinkin and Frank J.

Chloupek It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

|' Column 9 lines 4 to 11, delete the following structure? CH (CH CNHCHCH NCH CH NCH CH NCH CH NHLL'(CH CH OH OH OH R' R' R' Column 10, linesto 11, insert the following structure:

CH (CH CNHCH CH NCH l4 2 CH NCH Column 9, line 30, after the number 10-,delete "tri" and insert in place thereof --tris--.

CH NCH CH Signed and sealed this 6th day of March 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents l. .J

